FR2559494A1 - AQUEOUS PREPARATIONS FOR DYEING AND PRINTING MIXED FABRICS - Google Patents

Abstract

NEW AQUEOUS PREPARATIONS CONTAINING, IN ADDITION TO AT LEAST ONE INSOLUBLE TO DIFFICULTLY WATER-SOLUBLE COLORANT AND AT LEAST ONE FIBER-REACTIVE COLORANT, A NON-IONIC CELLULOSIC ETHER SOLUBLE IN WATER, ESSENTIALLY HYDROXYETHYLCELLULOSE, PREPARATIONS OBTAINED HAVING A VERY GOOD STORAGE STABILITY AND PRESENT NO RECRISTALLIZATION, NOR GIVING STICKY DEPOSITS. THE INVENTION FINDS ITS MAIN APPLICATION IN DYING AND PRINTING CELLULOSICS.

Description

AQUEOUS PREPARATIONS FOR DYEING AND PRINTING

MIXED FABRICS

  The invention relates to aqueous dye preparations, a process for their preparation and their use for dyeing and printing mixed fabrics.

polyester and cellulose.

  From DE 28 50 482 are known aqueous preparations of dyestuffs, insoluble dyes with poor water-soluble properties, which can be used for dyeing and printing synthetic textile materials, in particular

of polyester materials.

  It is also known from EP-A-0059782 and EP-A-0114031 that coloring preparations of reactive dyes can be used for dyeing and printing natural and synthetic fiber materials, essentially cellulose. If these two dye preparations are mixed for use in the dyeing and printing of mixed polyester and cellulosic fabrics, in this aqueous preparation, sticky sediments are formed in a short period of time which makes it impossible to industrial use of such preparations. It also occurs, in part, a

  recrystallization of the water soluble dye component.

  The invention now aims to eliminate these effects

undesirable.

  The inventors of the present invention have found that storage-stable mixtures, dispersed dye preparations and reactive dye preparations can be used when such mixtures are

  water soluble nonionic cellulosic ether.

  The invention accordingly relates to preparations

  aqueous solutions containing at least one insoluble dye with

  soluble in water and at least one fiber-reactive dye, and optionally other additives, characterized in that these preparations contain a non-cellulosic ether.

ionic soluble in water.

  In essence, they come into play as

  water-soluble nonionic cellulosic ether

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  ethylcellulose, in particular that having a molecular mass greater than 40,000, preferably greater than 150,000. A good stabilizing effect is obtained essentially with the hydroxyethylcelluloses whose average molecular mass is

4 6 5

  between 4.10 and 2.106, in particular between 1.5.10 and 1.106. In addition to hydroxyethylcellulose, water-soluble cellulosic ether can also be used essentially also methylcellulose, in particular that having a molecular weight.

4 5

  from 1.104 to 5.10 Cellulosic ethers of this kind, which occur alone or in mixtures, are used in a

  from about 1 to 10 g, especially from 3 to 7 g per kg of preparation.

  Essentially, they come into play as insoluble dyes that are difficult to dissolve in water.

  disperse dyes. It is then dyes of differ-

  classes, for example nitro dyes, aminoketone dyes, ketonimine dyes, methine dyes, nitrodiphenylamine dyes, quinoline dyes, aminonaphthoquinone dyes, coumarin dyes and in particular dyes anthraquinone and

  azo dyes, such as mononazole dyes and

  azo. It is also possible to use mixtures of different disperse dyes. However, it is advantageous to use the dye (diluted or undiluted) not as such, but in the form of an aqueous preparation which contains the dye (or dye mixtures) insoluble with difficulty in water soluble. We can

  to be used as aqueous preparations of this essential kind-

  those described in DE 28 50 482.

  Dyes which have one or more reactive radicals under dyeing conditions which, when dyes are applied to cellulosic materials, can be used as fiber-reactive dyes.

  can, in the presence of acid-binding substances, and possibly

  under the influence of heat, react with the groups

  hydroxyl of cellulose with formation of chemical bonds.

  We know from the literature a large number of

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  reactive groups with fibers of this kind. Among this large mass, there may be mentioned, for example, the reactive groups of the vinylsulfone group and their sulphonamide derivatives, but in particular the heterocyclic radicals, for example those having 2 or 3 nitrogen atoms in the heterocycle, such as those of the halogenotriazinyl series. , halogenoquinoxalinyl, halopyridazinyl and halopyrimidinyl, or the acyl radicals of halogenated aliphatic carboxylic acids or unsaturated carboxylic acids, such as the acyl radical of acrylic acid, or the radicals of the acid

  3-bromopropionic acid and 5-dibromopropionic acid.

  Examples of the fiber-reactive groups of the vinylsulfone series are, in addition to the vinylsulfonyl group proper, the aliphatic sulfone groups which contain in the e-position with respect to the sulfone group an alkali-removable group, such as an atom, halogen or a

  radical ester of an acid, such as for example the group B-chloro

  ethylsulfonyl, e-acetoxyethylsulfonyl, B- (3-sulfobenzoyloxy) -

  ethylsulfonyl, 6-sulfatoethylsulfonyl, e-thiosulfatoethyl-

  sulfonyl, e-phosphatoethylsulfonyl and e-sulfatoethylsulfonyl-

  methylamino, or the vinylsulfonylmethylamino group.

  The preferred reactive groups are, in particular, the acyl groups of carboxylic acids, or preferably heterocyclic groups, these groups containing at least one separable halogen atom under the conditions of the

dyeing.

  These are, for example, the following reactive groups: striazinyl radicals, which bear on the triazine nucleus one or two halogen atoms, for example chlorine, fluorine or bromine atoms, the pyrimidyl radicals which bear on the pyrimidine nucleus one to three halogen atoms, for example

  chlorine and / or fluorine atoms, or one or two aryl groups

  sulfonyl or alkanesulfonyl radicals, 2,3-dichloroquinoxaline

  or -6-carbonyl, or 2-chlorobenzothiazolyl. But these are mostly monochloro monofluoro-or dichloro-or difluoro-triazinyl, di- or trichloropyrimidinyl and difluorochloropyrimidinyl groups. It is advantageously a dye reactive with the fibers, which contains as reactive radical at least one heterocyclic group containing at least one separable halogen atom, such as preferably the dyestuffs of formula 1: D-Zn (1 D is the radical of a metalliferous or non-metalliferous azo dye, anthraquinone or phthalocyanine, which has one or more solubilizing group (s) in water, Z is a diazinyl or triazinyl group, which has at least one separable halogen atom, and optionally is attached to D by an amino group, and

n is 1 or 2.

  Dyestuffs of the formula la are also preferred: D-Z '(la), ## STR1 ## D has the meaning given for the formula I, and Z' is a group of the formula:

-N C C - (W) -1 R

I Cn-1H2n-1 NC / in which:

W is -

  Cq-1H2q-1 X is halogen, preferably C1 or F, Y is = N-, = CH- or = CX-, n is 1 or 2, preferably 1, p is 1 or 2, and q is 1 at 3, o, when p is 2; R is a lower alkyl, phenyl or naphthyl radical, optionally substituted, and when p is 1, R may be halogen, lower alkoxy, hydroxyalkoxy or alkoxyalkoxy, alkyl (lower) sulfonyl,

  optionally substituted phenoxy or -NH2.

  Another class of preferred reactive dyes

takes those of formula 2:

D'-Z '(2),

  in which D 'is the radical of a metalliferous or non-metalliferous azo dye, nitro, pyrazolone, thioxanthone, oxazine, anthraquinone, stilbene or phthalocyanine, containing one or more groups

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  solubilizers in water, and Z "is an acyl radical of a halogenated aliphatic carboxylic acid or an unsaturated carboxylic acid, and

n is 1 or 2.

  Reactive dyes containing sulfonic acid groups, as well as, optionally, their metal complexes, in the form of their metal salts, as obtained by synthesis, for example potassium, magnesium or essentially sodium. But they

  can also be used in the form of their amine salts.

  The reactive dyes may also be present in mixtures with each other, or possibly

with dyes of another type.

  It is also very advantageous to use dyes instead of aqueous dye preparations such as

  examples those described in EP-A-0059782 or EP-A-0114031.

  The aqueous preparations according to the invention can also contain, as additional additives, for example low silicone antifoaming agents and agents.

  antiseptics, for example based on phenol or cresol.

  The aqueous preparations according to the invention are stable at the temperature between 12 and 35 C, are perfectly stable at

  storage for more than 12 months, have no recrystalli-

  and do not give any sticky sediment. Their viscosity is between 300 and 1000 mPa.s; all this gives the printer the important advantage that he should only use one

  single preparation for dyeing poly-mixed fabrics

  ester and cellulosic materials, and that he is not obliged to

  use two or more preparations with different colors

rants, depending on the substrate.

  The preparation of these aqueous preparations can be carried out in various ways, for example: a) an aqueous preparation containing at least one insoluble dye which is hardly soluble in water is mixed with a non-ionic cellulose ether soluble in water in order to obtain a solution; water, solid or previously dissolved in water, and then an aqueous preparation containing at least one

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  dye reactive with the fibers, or b) mixing to obtain a solution an aqueous preparation containing at least one fiber-reactive dye with a non-ionic water-soluble cellulose ether, solid or previously dissolved in water, and then add an aqueous preparation containing at least one insoluble dye with little water-soluble, or c) add a soluble nonionic cellulose ether in

  water, solid or previously dissolved in water, at a prepa-

  aqueous solution containing at least one insoluble dye with

  caking soluble in water and at least one reactive dye with

fibers.

  The aqueous preparations according to the invention find an application for dyeing and printing mixed fabrics of polyester and cellulosic materials (regardless of the ratio

  mixture; for example 67:33, or 50:50).

  Then enter into account as subjects of

  fully synthetic or semi-synthetic substances

  high molecular weight, consisting of linear linear polyesters (generally polycondensation products)

  terephthalic acid and glycols, in particular ethylene-

  glycol, or polycondensation products of terephthalic acid and 1,4-bis (hydroxymethyl) hexahydrobenzene), as well as

  2 1/2-cellulose acetate and cellulose triacetate.

  Cellulosic materials are those derived from natural and regenerated cellulose, such as hemp,

  linen, jute, viscose, fibranne and in particular cotton.

  The polyester / cellulose blended fabric may be, for example, in the form of a fabric, a mesh fabric such as a

  hosiery article or knit, or nonwoven fabric.

  The textile material (blended fabric) may be in a known manner printed with the printing paste or padded with a padding bath, and then dried. The dyes are then fixed on the mixed fabric, for example by heating for 30 to 120 seconds at 190 to 225 ° C, preferably for 60 seconds at 210 ° C, or by steaming, for example at atmospheric pressure with steam. overheated at 170 to 2000C for 3 to 12, preferably 5 to 8 minutes, or with

7 2559494

  water vapor under an overpressure of 1.5 bar for 15 to 30 minutes.

  After fixing, we finish the operations as usual.

  This process produces prints or dyes united with good dye yield and a dye tone on tone very close. The examples below serve to explain the invention. Parts are parts by weight; the percentages are given

  in percentages by weight and temperatures in degrees Celsius.

  Obtaining the aqueous preparation An aqueous solution of hydroxyethylcellulose (average molecular weight 5, 5.6 × 10 5) is added with stirring at ambient temperature to an aqueous preparation a) containing at least one insoluble dye with hardly any water soluble solution. (We

  This solution is obtained by mixing with stirring

  ethylcellulose powder with water at room temperature for 45 to 60 minutes; the viscosity of this solution is about 48,000 mPa. s (Brookfield, 20 rpm, spindle N 6)). Then

  an anti-foaming agent (low silicon content) is added.

  cone, based on 2-ethyl-n-hexanol). Then, with continuous stirring, an aqueous preparation b) containing at least

  a dye reactive with the fibers, and stirring is continued.

  A fluid ready-to-use preparation is obtained, none of which

  Sticky sediment does not separate even after prolonged rest.

  Preparations a) and b) coming into use, and their

  quantities are given in the table below.

BOARD

  Example Preparation a) Amount of Preparation b) Amount of Quantity of Hydroxyethyl-

  preparation a) preparation b) 1 Preparation al) 13.8 parts Preparation b1) 63.1 parts 23.1 parts of a solution

3% aqueous.

  2 Preparation a2) 17.7 parts Preparation b2) 59.2 parts 23.1 parts of a solution

3% aqueous.

  3 Preparation a3) 22.7 parts Preparation b3) 60.6 parts 16.7 parts of a solution

3% aqueous.

  4 Preparation a4) 27.1 parts Preparation b4) 56.2 parts 16 parts of a solution

3% aqueous.

  Preparation a5) 26.4 parts Preparation b5) 73.3 parts 0.3 part in the form

a powder.

  6 * Preparation a6) 22.2 parts Preparation b6) 51.9 parts 14.8 parts of a solution

3% aqueous.

  The preparation of Example 6 further contains 11.1 parts of water.

ri vi Ln va

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  Preparations al) to a6) and b1) to b6) have the following composition: Preparation a1) 440 parts of the disperse dye of formula (101) C1 CH30- / vN- / ≤ (101)

O2. '-.CH3

  in the form of dried cake, low in electrolytes, lignin parts for sulfonated kraft (molecular weight

6000 to 50 000);

  parts of an ethylene oxide / nonionic propylene oxide block copolymer (molecular weight about 16,500); parts of 1,2-propylene glycol; 348 parts of water and

2 parts of an antiseptic agent.

  Preparation a2) 42 parts of the disperse dye of formula (102) o011 4-. C2H4CN 202N-a (102)

25. = - - - = - -C2H40C2H4CN

  (crude dye with low electrolyte content); 2 parts of lignin for sulfonated kraft (molecular weight 2000 to 30,000); 2 parts of ethylene oxide / nonionic propylene oxide block copolymer (molecular weight about 16,000); 17 parts of 1,2-propylene glycol; 36 parts of water and

2 parts of an antiseptic agent.

  Preparation a3) About 30 parts of the disperse dye of formula (103)

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  sa9 02N-00 \ -N-N-e <-NHCHztHCHz-0 - e (103) \ 0 _ = \ _ / \ _ = i

C1 SIHCOCH3

  2 parts lignosulphonate; 4 parts of a block copolymer ethylene oxide / propylene oxide (80% ethylene oxide, 20% propylene oxide); 18 parts of 1,2-propylene glycol and

parts of water.

  Preparation a4) It consists of a mixture of two dye preparations, namely: 19 parts of a preparation having the following composition: 26.3% of the blue dye of formula e (104a)% f'z! ## STR5 ## with O, 22.4% 1,2-propyleneglycol moieties; 3% of an ethylene oxide / propylene oxide block copolymer (molecular weight = 16,500); 2% of lianosulphonate (molecular weight 6000 to 50,000); 0.9% of an antiseptic agent; 0.5% of an antifoam agent; 44.9% of water, and 8.1 parts of a preparation having the following composition: 41.5% of the violet dye of formula (104b)

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  ## EQU1 ## where ## EQU1 ## 17.8% 1,2-propyleneglycol; 3% of an ethylene oxide / propylene oxide block copolymer (molecular weight about 16,500); 1.6% lignosulfonate (molecular weight 6000 to 50,000); 0.8% of an antiseptic agent; 0.1% of a thickener; 0.3% of an antifoam agent;

% of water.

  Preparation a5) It consists of a mixture of two preparations of dyes, namely: 21.9 parts of a preparation having the following composition: 0% of the red dye of formula (105a) ## EQU1 ## / \ _ / o ot 254. N- \ - / O \. (105a) CzH40COCH3 21% 1,2-propylene glycol; 3% of an ethylene oxide / propylene oxide block copolymer (molecular weight about 16,500); 1.5% lignosulfonate (molecular weight 6000 to 50,000); 0.7% of an antiseptic agent; 0.2% of an antifoam agent; 43.6% of water, and 4.5 parts of a preparation having the following composition: 41.5% of the violet dye of formula (105b)

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  t. ## STR1 ## 17.8% of 1,2-propylene glycol; 3% of an oxidized ethylene / propylene oxide block copolymer (molecular weight about 16,500); 1.6% lignosulfonate (molecular weight 6000 to 50,000); 0.8% of an antiseptic agent; 0.1% of a thickener; 0.3% of an antifoam agent;

35% water.

Preparation a6)

  38 parts of the disperse dye of formula (106) -

  - CzHi.CN o.N-. <.- O - *. - (106) 20. =. C0H40C1H4CN 2 parts oxilignosulphonate; 3 parts of a block copolymer of ethylene oxide and propylene oxide (80% ethylene oxide and 20% propylene oxide); 18 parts of propylene glycol; 0.05 part of an antifoam agent; 1 part of an antiseptic agent;

37 parts of water.

  Preparation b1) 22.1 parts of the reactive dye of formula (107) 1 a \. S03Na

N _ \. \ / * OI.C2H5

  =. / \ .. N-. __. = o (_o_) SO3Na \ ChI = \ CHS-3Na

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  0.2 parts of disodium hydrogenphosphate, and

about 70 parts of water.

  Preparation b2) About 23 parts of the reactive dye of formula (108) S? 3Na? H l

AT/.,% /.'..* *% \

  I I! 1N-N-. Ia (108) S3Na SO3Na 1.5 parts of sodium tripolyphosphate;

, 5 parts of water.

  Preparation b3) About 25 parts of the reactive dye of formula (109) ## STR3 ## where: ## STR2 ## 4 !. / N! +, / \. vs C (109) SO3Na SO3Na 1.5 parts of sodium tripolyphosphate; 0.15 part of sodium dihydrogenphosphate;

73 parts of water.

  Preparation b4) 27.8 parts of the reactive dye of formula (110) S \ 3Na Ck3 / SO3Na

AT / '%. N 4 \\ ./- "C"

  HZN-a-NH-. * CH3 N9SO3Na (110) = C13 NH <2 -Nil-. o

._ /. -

  1.6 parts of disodium hydrogenphosphate; 0.8 parts of potassium hydrogen phosphate;

69.1 parts of water.

  Preparation b5) 26.3 parts of the reactive dye of formula (111)

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S03Na

/'%-=-.-N.-.-.-, -.

Ili \ _. / \ I / (111)

\ N- \ 'NH

* / = '\ / ='

  LO. . 0.01 part of disodium hydrogenphosphate 0.8 part of potassium dihydriganophosphate;

71.3 parts of water.

  Preparation b6) 19-20 parts of the reactive dye of formula (112) / SO3Na? H

H3CO -. (- '4 -NN).

NaO3S. *.

  2 parts of sodium tripolyphosphate;

78 parts of water.

  We get equally good preparations when we

  mix together preparations a and b) correspondingly

  and that is introduced into this mixture, slowly and

  stirring, hydroxyethylcellulose in powder form.

Example 7

  17.6 parts of an aqueous dispersed dye preparation having the following composition:% dye of formula (113a)

I you*.

\ = /, =. NO <-N-- (113a) o / \.

\ S02N \ _

C2HOCOCH3

  1.5% oxylinosulphonate; 3% of a block copolymer of ethylene oxide and propylene oxide (molecular weight about 16,000); 0.7% of an antiseptic agent;

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  21% 1,2-propylene glycol; 0.2% of an antifoam agent; 43.6% of water, and 3.6 parts of a disperse dye preparation having the following composition: 41.5% of the violet dye of formula (113b) 11./ 11 "1 (113b)

I IU I

%. / *. /. '

  17.8% 1,2-propylene glycol; 3% of a block copolymer of ethylene oxide and propylene oxide (molecular weight about 16,000); 1.6% lignosulfonate (molecular weight 6000 to 50,000); 0.8% of an antiseptic agent; 0.1% of a thickener; 0.3% of an antifoam agent; % water are completed with stirring with 20 parts of a 5% aqueous solution of methylcellulose (average molecular weight of methylcellulose about 200,000). 58.8 parts of an aqueous reagent dye preparation, having the following composition: 26.3% of the dye of formula (114) SO3Na ..... N = N-, are then added with stirring. N-Ni (114) embedded image 1.6% of disodium hydrogenphosphate; 0.8% potassium dihydrogenphosphate;

71.3% water.

  A fluid and homogeneous dye preparation is obtained (viscosity 750 mPa.s at the Brookfield LVT viscometer, spindle N 2, rpm). The dye preparation has a pH of about 7.8 and

  is perfectly stable in storage. Without the addition of methyl

  cellulose, it is formed on the other hand, even after storage of

  short-lived, sticky sediment.

  Example 8 (printing process) A polyester / viscose fabric (67:33) is printed as follows

we blend: -

  930 parts of a parent containing, per 1000 parts: 660 parts of water, 5 parts of an emulsifier for oil-in-water emulsions based on an oxy-ethyl fatty acid, parts of White Spirit (mixture alkanes having a boiling point of 150 to 190 ° C), parts of sodium alginate, 100 parts of urea and parts of sodium bicarbonate, to 70 parts of a dye preparation according to Example 1, and printing the mixed fabric with this printing paste on a rotary frame printing machine. Then we dry

  at 90 and fixed with hot air at 205 for 75 seconds.

  Then we wash. A brilliant yellow print is obtained with good sharpness of the contours, good solidity and

good tone-on-tone coloring.

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Claims (9)

claims   Aqueous preparations containing at least one insoluble dye with low water-soluble content and at least one fiber reactive dye, and optionally other additives, characterized in that these preparations contain a   water soluble nonionic cellulosic ether.   2. Aqueous preparations according to claim 1, characterized   contained in that they contain as cellulosic ether of hydroxyethylcellulose.   3. Aqueous preparations according to claim 1, characterized   contained in that they contain as cellulosic ether methylcellulose.   4. Aqueous preparations according to claim 2, characterized   in that hydroxyethylcellulose has a molecular weight greater than 40,000.   5. Aqueous preparations according to claim 2, characterized   in that hydroxyethylcellulose has a molecular weight greater than 150 000.   6. Aqueous preparations according to claim 1, characterized   in that they contain 1 to 10 g of the cellulose ether   water soluble nonionic acid per kg of preparation.   Aqueous preparations according to claim 1, characterized   in that they contain 3 to 7 g of the cellulose ether   water soluble nonionic acid per kg of preparation.   8. Process for obtaining aqueous preparations according to claim 1, characterized:   (a) in that, to obtain a solution, a mixture is prepared   aqueous solution containing at least one insoluble dye with   cilium soluble in water with a water-soluble, non-ionic cellulose-soluble ether or previously dissolved in water, and then adding an aqueous preparation containing at least one fiber-reactive dye, or   (b) mixing to obtain a solution   aqueous composition containing at least one fiber-reactive dye with a water-soluble, non-ionic, non-ionic cellulosic ether previously dissolved in water, and then adding an aqueous preparation containing at least one insoluble, hardly soluble dye in the water, or 18 - 2559494   c) in that a water-soluble non-ionic cellulose ether, solid or previously dissolved in water, is added to an aqueous preparation containing at least one insoluble dye with hardly any water-soluble substance and at least one dye reactive with the fibers.   9. Use of the aqueous preparation according to the claim   1 or the preparation obtained according to claim 8, for dyeing and printing mixed polyester fabrics. and cellulosic materials.